Process for dyeing cellulose fibres

ABSTRACT

1. IN A PROCESS FOR PAD-DYEING TEXTILE MATERIALS MADE OF OR CONTAINING NATIVE OR REGENERATED CELLULOSE FIBERS WITH DYESTUFFS HAVING AS GROUP CAPABLE OF REACTING WITH THE HYDROXYL GROUPS OF THE FIBER AT LEAST ONE B-(2,2,3,3TETRAFLUORO - CYCLOBUTYL) - ACRYLOYLAMINO OR VINYLSULFONE GROUP OR SULFATOETHYLSULFONE OR THIOSULFATOETHYLSULFONE GROUP, AND FIXING THE DYESTUFFS ACCORDING TO THE DWELLING METHOD, THE IMPROVEMENT WHICH COMPRISES: USING IN SAID PROCESS, PADDING LIQOURS CONTAINING, IN ADDITION TO THE SAID DYESTUFFS AS AN AGENT HAVING ALKALINE REACTION, A LIQUID SODIUM SILICATE HAVING A CONCENTRATION IN THE RANGE OF FROM 37* TO 60*BE., CORRESPONDING TO AN SIO2-CONTENT OF THE AQUEOUS SOLUTION OF 27.2 TO 38.2 PERCENT BY WEIGHT, IN AN AMOUNT RANGING FROM 25 GRAMS TO 350 GRAMS PER LITER OF PADDING LIQOUR.

United States Patent slgnor t0 Farbwerke Hoeehst Aktiengesellschaftvormals Meister L Germany ucrus & Brumng, Frankfurt am Main,

0 Drawing. Continuation of abandoned application Ser No. 706 76 F 1970Se}. N3. Sig-1525?, 1968. This application Oct. 12,

Claims priority, 21

pplrcatron German F 51,665; Apr. 12, 1967,F 52 l i] 6 1967 Int. o I) 4U's. L l 2, l

C L 5 C arms ABSTRACT OF THE DISCLOSURE Process for pad-dyeing textilemate V ria ggrtlgsenaerated cellulose fibres with radii/35 562512332groups of tggotg?) capable of reacting'with the hydroxyl butynlacr 1e 1re at least one ,8-(2,2,3,3-tetrafluorocycloone groupyfgy amino or avmylsulfone group or at least group by usiin ng 1n an alkaline medium avinyl-sulfone in addition to sald process padding liquors containinghavin 11k 1 e above -mennoned dyestuffs as a ent g t a me action allquid alkali metal silicate g s is a continuation of a l' N22. 7 26 7 6512d Feb. an, 1968, now aba iici iiif Sen fibres can be d slat textllematerials made of cellulose ponent ca ablye with reactive dyestuffshaving as comcyclobut 1)p e of reacting the ,B-(2,2,3,3-tetrafluor groupf0yrm-izrilcryloylammoor vinylsulfone group or a group by anog n thepresence of alkalies a vinylsulfone alkali-136 conafiii 535F332 iiifol ldyestuffs under lose fibres. As agents having alkaliri e 233121222311example, as soda, sodiuni b iphate, sodium hydroxide, sodi- Thisapplication ondar y reaction, more or less large portions of the dyestuff u the strifh ge r i11 eilligiie i e id dyeing In this instance ,us

of the bath and the longer t the higner the temperature g period playsan ahty of the dyeings working, the dyeing nta ner or a preparin addingmachine. Thi;

especially important rol e in th prepared. Withln this method of2115232111 led gradually into the p batcherse,arehc;]wever, has negativeeffects wh n l is necessar yed for Wl'llCh a large amount of a d abgerabout mor y,thso that occasionally a time differ ye ath e an one hourbetween the applicatior i i ti i O C., as rs often the case in countrieshaving a hot climate.

p ice metering pumps or mixing devices are brought into action in suchpadding processes m which, generally, relatively large amounts of strongalkalies (for example sodium hydroxide or sodium metasihcate) are usedand in which-especially when large batches are dyed-the dyebath isabandoned partially for, a prolonged period of time in the preparingvessel. Sa1d arrangements allowthe dissolved dyestuffs to be broughtinto contact with the alkali only shortly before they are introducedinto the padding machine (cf. Textil-Praxls, 1963, page v1189). Adisadvantage of this process, how, ever, is that only few dye-housespossess such metering pumps or mixing devices, which is due to the hlghpurchase price for such devices. t

An important padding process for fixing the above mentioned dyestuffs onfabrics made of cellulosefibres is in this respect the so-calledpad-batch-process or a variation thereof, the so-called"pad-short-dwell-process (cf. SVF-Fachorgan 1961, page 320, as well asTextil- Praxis 1963, page 1189). According to these processes thetextile material is wound up on a roller and allowed to dwell, the woundup textile material being, during the dwelling time, hermeticallyenveloped in order to prevent the carbon dioxide from the air reactingwith the alkalies at the edges of the rolled up material, which wouldthen result in only an insufficient dyestufi fixation in these areas. Itis also possible in the above-mentioned processes, to work without ametering pump, but only weak alkalies such, for example, as soda oralkali metal bicarbonate are allowed then to be used. These substances,however, reduce the colour yield due to the insufficient fixation quoteof the dyestuffs on the fibre. Furthermore, the applica: tion of weakalkalies in this process may run the risk that, particularly when dyeinggreater batches, the edges of the initial portion of the padded,rolled-up material become lighter coloured on account of the long periodduring which the textile material is rolled up.

A further disadvantage of the pad-batchor the padshortdwell-process liesin the fact that after dwelling, when drying the textile materialwithout preceding acidification of the goods, the colour yieldisreduced, owing to cleavage of the dyestuff-fibre-linkage. Therefore itis inappropriate to use the non after-treated textile material in theprinting. t a

It has now been found that textile materials made of native orregenerated cellulose fibres can be dyed according to the paddingprocess with reactive dyestuffs having as a group capable of reacting atleast one {3-(2,2,3,3- tetrafluoro-cyclobutyl)-acryloylarnino group or avinylsulfone group or at least one group forming in an alkaline medi uma vinyl sulfonegroup, by using in said process padding Therefore liquorscontaining besides the above-mentioned dyestuffs as agents havingalkaline action a liquid alkali metal silicate. For the fixation of thedyeings, the padded material is allowed to dwell at temperatures of upto 100 C., preferably at room temperature, the fabric being wound up ona roller or piled up. The dwelling period is generally between 1 hourand 30 hours.

By the addition of alkali metal silicate (water glassy when carrying outthe process of the present invention a- As reactive dyestuffsrepresentatives of the various organic dyestuff classes can be usedaccording to the present invention, for example azoand anthraquinonedyestuffs, containing either at least oneB-(2,2,3,3-tetrafluoro-cyclobutyl)-acryloylaminoor a vinylsulfone groupor at least one group which can be converted into a vinylsulfone groupwhen exposed to alkaline agents during the dyeing process. Theappropriate azo dyestuffs may, if desired, be used in metallized form.

As examples for such groups in the dyestuffs to be applied which can beconverted into the vinylsulfone group in the presence of substanceshaving alkaline reaction during the dyeing process, there are mentionedin particular the sulfuric acid ester or thiosulfuric acid ester offi-hydroxyethylsulfone groupings.

Of the liquid alkali metal silicates (water-glasses) which are added tothe padding baths according to the process of the present inventionthere are suitably used the commercial sodium silicates (soda waterglass). Preferably there are used sodium silicates having aconcentration of about 37 to about 60 B., corresponding to an SiO-content of the aqueous solution of about 27.2 to about 38.2 percent byweight.

The amount of the fixing agent used depends on the concentration of thealkali metal silicate applied, on the dyestuif concentration and on thenature of the dyestutf, and ranges generally from about g. to about 350g., preferably from about 50 g. to 200 g. per liter of padding bath.Furthermore, it is possible to add to the dye baths still a sodiumhydroxide solution besides the silicate, but the amount of sodiumhydroxide solution (referred to sodium hydroxide solution of 38 B.) isnot to exceed 10% of the amount of alkali metal silicate used, sinceotherwise the stability of the bath is reduced.

The technical advantage which is achieved when using liquid alkali metalsilicates as fixing agents lies in the fact that sources of error areavoided which are possible when preparing the conventional aqueouspadding liquors, an excellent reproducibility of the desired tints isguaranteed, and the dyeings do not suffer a change of shade during thedwelling period. It is surprising that with the process of the presentinvention, besides an excellent colour yield and levelness of thedyeing, still an excellent tone-in-tone dyeing on mixed fabrics made ofnative or regenerated cellulose fibre is obtained which is superior tothat according to known conventional processes when other alkalies areused such, for example, as sodium hydroxide solution, trisodiumphosphate, soda, an alkali metal bicarbonate or metasilicate.

The following Examples serve to illustrate the invention but they arenot intended to limit it thereto.

EXAMPLE 1 A cotton poplin is padded in a padding machine-without using ametering pump or mixing deviceat a squeezing effect of 70 percent byweight with a padding liquor of C. containing per liter of water 10* g.of the dyestuif of the formula ease 4 EXAMPLE 2 A mercerized cottonfabric is padded in a padding machinewithout using a metering pump or amixing device-at a squeezing effect of percent by weight with a paddingliquor of 20 C. containing per liter of water 20 g. of the dyestuif ofthe formula H0 5 SO3H in commercial form and condition, and 200 g. ofsodium silicate of 49 B. After padding the fabric is rolled upcontinuously and allowed to dwell at 20 C. for 6 hours. Then the dyedgoods are rinsed, acidified and soaped.

There is obtained a brillant orange dyeing of an excellent colour yieldand having level coloured ends and edges.

EXAMPLE 3 A mercerized cotton fabric is padded in a paddingmachinewithout using a metering pump or a mixing deviceat a squeezingeffect of 80 percent by weight with a padding liquor of 20 C. containingper liter of Water 40 g. of the dyestuff of the formula in commercialform and condition, and 50 g. of sodium silicate of 49 B. After paddingthe fabric is rolled up continuously and allowed to dwell at 20 C. for24 hours. Then the dyed goods are rinsed as usual, acidified and soaped.

There is obtained a brilliant violet dyeing of an excellent colour yieldand having level coloured ends and edges.

EXAMPLE 4 A mercerized cotton fabric is padded in a paddingmachinewithout using a metering pump or a mixing device-at a squeezingeffect of 80 percent by weight with a padding liquor of 30 C. containingper liter of water 20 g. of the dyestuff of the formula SO H incommercial form and condition, and 300 g. of sodium silicate of 49 B.After padding the fabric is rolled up continuously and allowed to dwellat 30 C. for 6 hours. Then the dyed goods are rinsed as usual, acidifiedand soaped.

There is obtained a brilliant yellow dyeing of an excellent colour yieldand having level coloured ends and edges.

Example 5 A mercerized cotton fabric is padded in a paddingmachinewithout using a metering pump or a mixing deviceat a squeezingeffect of 80 percent by weight with a v .padding liquor of3 C.containing per liter of water 30 g. of the dyestutf of the formula,colgur yield and having level coloured ends and edges.

. ,,."If, ,in the Example described above, after dwelling, the fabric is.d riedfor-(J. minutes'at 140 C. and then rinsed, acidified and soaped,as usual, a level dark blue dyeing is obtained likewise; re-cleavage ofthe dyestuif-fibre-linkage, caused while drying, could not beascertained from the colouristic aspect. Example 6 I I 'A fabric 'made'of staple fibre is padded in a padding machinewithout using'a meteringpump or a mixing 'deVice at a squeezing effect of 90 percent by weightwith a padding liquor-of 20 C. containing per liter of Water '40 g.-- ofthe dyestulf of the formula in commercial form and composition, and 200g. of sodium silicate of 49 B. After padding the fabric is rolled upcontinuously and allowed to dwell at 20 C. for 8 hours. Then the dyedgoods are rinsed as usual, acidified and soaped.

There is obtained a brilliant red dyeing of an excellent colour yieldand having level coloured ends and edges.

Example 7 A cotton fabric is padded in a padding machinewithout using ametering pump or a mixing device-at a squeezing effect of 80 percent byweight with a padding liquor of 20 C. containing per liter of water 70g. of the dyestutf of the following formula in commercial form andcomposition, and 150 g. of sodium silicate of 49 B. After padding thefabric is rolled up continuously and allowed to dwell at 20 C. for 18hours. Then the dyed goods are rinsed, acidified and soaped, as usual.

There is obtained a blue dyeing of an excellent colour yield and havinglevel coloured ends and edges.

Example 8 A mixed fabric of staple fibre and cotton in a mixingproportion of 30:70 is padded in a padding machinewithout using ametering pump or a mixing device-at a squeezing effect of 80 percent byweight with a padding in commercial form and composition, and 200 g. ofsodium silicate of 49 B. After padding the mixed fabric is rolled upcontinuously and allowed to dwell at 30 C. for 8 hours. Then the dyedgoods are rinsed as usual, acidified and soaped.

There is obtained a yellow tone-in-tone dyeing of an excellent colouryield having level coloured ends and edges.

Example 9 A staple fibre fabric is padded in a paddingmachine at asqueezing effect of 90 percent by weight with a padding liquor of 40 C.containing per liter of water 20 g. of the dyestulf of the formula OsHin commercial form and composition, 50 g. of sodium silicate of 49 B and5 cc. of a sodium hydroxide solution of 38 B. After padding the fabricis rolled up continuously and allowed to dwell at 40 C. for 24 hours.Then the dyed goods are rinsed, acidified and soaped, as

usual. I

There is obtained a brilliantorange dyeing having level coloured endsand edges.

Example 10 A mercerized cotton fabric is padded in a padding machine ata squeezing effect of 60 percent by Weight with a padding liquor of 30C. containing per liter of Water 20 g. of the dyestuff of the formulaS0311 OH NHC OCH=CHCHOH:

Example 11 A bleached linen fabric is padded in a padding machine at asqueezing effect of percent by weight with a padding liquor of 20 C.containing per liter of water 15 g. of the dyestuff of the formula I I II GF2CF2 N=N I HOSa SOaH A mercerized cotton fabric is padded in. apadding machine at a squeezing effect of 60 percent by weight with apadding liquor of 20 C. containing per liter of water 20 g. of thedyestulf of the formula in commercial form and composition, and 200 g.of sodium silicate of 49 B. After padding the fabric is rolled upcontinuously and allowed to dwell at 20 C. for 24 hours.

There is obtained a yellow dyeing having level coloured ends and edges.

Example 13 A mercerized cotton fabric is padded in a padding machine ata squeezing effect of 60 percent by weight with a padding liquor of 20C. containing per liter of water 30 g. of the dyestufi' of the formula g0111 in commercial form and composition, and 50 g. of sodium silicate of49 B. After padding the fabric is rolled up continuously and allowed todwell for 24 hours.

There is obtained a yellow dyeing having level coloured ends and edges.

1. In a process for pad-dyeing textile materials" made of or containingnative or regenerated cellulosefibers with dyestuffs having as groupcapable of reacting with the hydroxyl groups of the fiber at least oneii-(2,23,3- tetrafluoro cyclo'butyl) acryloylamino or vinylsulfone groupor sulfatoethylsulfone or thiosulfatoethylsulfone group, and fixing thedyestuffs according to the dwelling method, the improvement whichcomprises: using in said process, padding liquors containing,in'addition to the said dyestuffs, as an agent having alkaline reaction,a liquid sodium silicate having a concentration in the range of from 37to B corresponding to an SiO -content of the aqueous solution of 27.2 to38.2 percent byweight, in an amount ranging from 25 grams to 350 gramsper liter of padding liquor. I v

2. A process as claimed in Claim 1, wherein the liquid sodium silicateis used in an amount of from 50 gra'ms'to 200 grams per liter of paddingliquor. I

3. A process as claimed in Claim 1, wherein padding liquors are usedwhich additionally contain a sodium hydroxide solution, the amountthereof, calculated as' so'cli um hydroxide solution of 38 B., notexceeding ten percent by weight of the amount of sodium silicate used.

4. A process as claimed in Claim 1, wherein for the fixation of thedyeings, the textile material padded with reactive dyestuff and sodiumsilicate is batched up on a roller and is allowed to dwell there attemperatures rang ing from room temperature up to C.

5. A process as claimed in Claim 1, wherein for the fixation of thedyeings, the textile material padded with reactive dyestuif and sodiumsilicate is cuttled up and'is allowed to dwell there at temperaturesranging from room temperature up to 100 C.

References Cited UNITED STATES PATENTS 3,232,927 2/ 1966 Randall et al.260163 3,129,052 4/ 1964 Dawson et al 854 3,360,505 12/1967 Scherer etal. 260-447 ROLAND E. MARTIN, JR., Primary Examiner U.'S. Cl. X.R.

81 P, 1 Q, 39, 41 R, 42 R, 82

1. IN A PROCESS FOR PAD-DYEING TEXTILE MATERIALS MADE OF OR CONTAININGNATIVE OR REGENERATED CELLULOSE FIBERS WITH DYESTUFFS HAVING AS GROUPCAPABLE OF REACTING WITH THE HYDROXYL GROUPS OF THE FIBER AT LEAST ONEB-(2,2,3,3TETRAFLUORO - CYCLOBUTYL) - ACRYLOYLAMINO OR VINYLSULFONEGROUP OR SULFATOETHYLSULFONE OR THIOSULFATOETHYLSULFONE GROUP, ANDFIXING THE DYESTUFFS ACCORDING TO THE DWELLING METHOD, THE IMPROVEMENTWHICH COMPRISES: USING IN SAID PROCESS, PADDING LIQOURS CONTAINING, INADDITION TO THE SAID DYESTUFFS AS AN AGENT HAVING ALKALINE REACTION, ALIQUID SODIUM SILICATE HAVING A CONCENTRATION IN THE RANGE OF FROM 37*TO 60*BE., CORRESPONDING TO AN SIO2-CONTENT OF THE AQUEOUS SOLUTION OF27.2 TO 38.2 PERCENT BY WEIGHT, IN AN AMOUNT RANGING FROM 25 GRAMS TO350 GRAMS PER LITER OF PADDING LIQOUR.